JPH05214266A - Self-depositing water-based coating composition - Google Patents
Self-depositing water-based coating compositionInfo
- Publication number
- JPH05214266A JPH05214266A JP4040571A JP4057192A JPH05214266A JP H05214266 A JPH05214266 A JP H05214266A JP 4040571 A JP4040571 A JP 4040571A JP 4057192 A JP4057192 A JP 4057192A JP H05214266 A JPH05214266 A JP H05214266A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- coating composition
- acid
- coating
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/088—Autophoretic paints
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水分散性または水溶性
の有機被膜形成用樹脂、フッ化物イオンおよび／または
錯フッ化物イオン、亜鉛、コバルト、マンガン、ニッケ
ル、鉄、およびアルミニウムの金属イオンから選ばれる
１種または２種以上のイオンを含み、さらにタングステ
ン酸イオンおよび／またはモリブデン酸イオンを含有
し、ｐＨが約１．６〜５の酸性コーティング組成物に、
金属表面、例えば鉄系金属、亜鉛系金属、アルミニウム
系金属、およびマグネシウム系金属等の表面を接触させ
ることにより、該金属表面にすぐれた付着性、および耐
食性を有する樹脂被膜を形成せしめることができる自己
析出型水性コーティング組成物に関する。The present invention relates to a water-dispersible or water-soluble resin for forming an organic film, a fluoride ion and / or a complex fluoride ion, a metal ion of zinc, cobalt, manganese, nickel, iron and aluminum. An acidic coating composition containing one or more ions selected from the above, further containing tungstate ion and / or molybdate ion, and having a pH of about 1.6 to 5,
By contacting a metal surface, for example, an iron-based metal, a zinc-based metal, an aluminum-based metal, a magnesium-based metal, or the like, a resin coating having excellent adhesion and corrosion resistance can be formed on the metal surface. An autodeposition aqueous coating composition.
【０００２】[0002]
【従来技術】金属表面を有機被膜用樹脂を含む酸性のコ
ーティング組成物に接触させることによって、該金属表
面に樹脂被膜を形成せしめることができるコーティング
組成物は、自己析出型コーティング組成物として知られ
ており、特公昭４７−１７６３０号、特公昭４８−１４
４１２号、特公昭５２−２１００６号、特公昭５２−３
５６９２号、特公昭５３−１５０９３号、特公昭５３−
４４９４９号、特開昭６０−５８４７４号、特開昭６１
−１６８６７３号、および特開昭６１−２４６２６７号
等の公報に開示されている。2. Description of the Related Art A coating composition capable of forming a resin film on a metal surface by contacting the metal surface with an acidic coating composition containing a resin for an organic film is known as an autodeposition coating composition. , Japanese Patent Publication No. 47-17630, Japanese Patent Publication No. 48-14
No. 412, Japanese Patent Publication No. 52-21006, Japanese Patent Publication No. 52-3
5692, Japanese Patent Publication No. 53-15093, Japanese Patent Publication No. 53-
44949, JP-A-60-58474, JP-A-61.
No. 168673 and Japanese Patent Application Laid-Open No. 61-246267.
【０００３】公知のコーティング組成物の特徴は、コー
ティング組成物中に清浄な金属表面を浸漬することによ
り、浸漬時間とともに厚さあるいは重量が増大する樹脂
被膜を形成せしめることができることである。さらに
は、被膜形成は該金属表面上のコーティング組成物の化
学作用（エッチングにより金属表面から溶出した金属イ
オンにより樹脂粒子が会合して金属表面上に析出する）
により達成されるため、電着のごとく外部からの電気を
使用することなく、該金属表面上に樹脂被膜を効果的に
形成せしめることができることである。A feature of known coating compositions is that immersion of a clean metal surface in the coating composition can form a resin coating which increases in thickness or weight with immersion time. Further, the film formation is a chemical action of the coating composition on the metal surface (metal particles eluted from the metal surface by etching cause resin particles to associate and deposit on the metal surface).
Therefore, the resin coating can be effectively formed on the metal surface without using electricity from the outside such as electrodeposition.
【０００４】コーティング組成物に金属イオンを含有し
た例は、第２鉄イオンを供給しうる鉄化合物を含有した
組成物により鉄系金属をコーティングすることが特公昭
５２−３５６９２号に開示されている。さらに各種金属
素材へのコーティング組成物として各種金属イオン（第
２鉄イオンを除く）を含有した組成物が特公昭５３−４
４９４９号に開示されている。近年、形成される被膜、
特に付着性、耐食性に対し、より高性能が要求されてい
る。米国特許第３，６４７，５６７号、同第４，０３
０，９４５号、特公昭５３−１５０９３号、および特開
昭６１−１６８６７３号で開示されているように、形成
される被膜に、より良好な付着性および耐食性を付与す
るため、被膜のキュア以前（焼付乾燥以前）にクロム含
有溶液やアルカリ水溶液等によるリンス処理（自己析出
直後の後処理）が施されている。被膜性能、特に耐食性
に関してはクロム化合物の含有が有効である。An example of a coating composition containing metal ions is disclosed in Japanese Patent Publication No. 52-35692, in which an iron-based metal is coated with a composition containing an iron compound capable of supplying ferric ions. .. Further, as a coating composition for various metal materials, a composition containing various metal ions (excluding ferric ion) is disclosed in Japanese Examined Patent Publication No. 53-4.
No. 4949. Coatings formed in recent years,
In particular, higher performance is required for adhesion and corrosion resistance. U.S. Pat. Nos. 3,647,567 and 4,03
As disclosed in Japanese Patent Publication No. 0,945, Japanese Patent Publication No. 53-15093, and Japanese Patent Application Laid-Open No. 61-168673, in order to impart better adhesion and corrosion resistance to the formed film, before the film is cured. Before (baking and drying), a rinsing treatment with a chromium-containing solution, an alkaline aqueous solution, or the like (post-treatment immediately after self-deposition) is performed. Containing a chromium compound is effective for coating performance, especially for corrosion resistance.
【０００５】しかしながら、クロムリンス等によるクロ
ム化合物の使用は、環境上あまり好ましくない。近年、
金属等の塗装は、クロム化合物を含有しないコーティン
グ組成物の使用への要求が高まっている。さらに工程短
縮の要求もある。クロム化合物を含有することなく、形
成される被膜の付着性および耐食性を向上させることが
重要な課題である。従来のクロム化合物を含有しないコ
ーティング組成物から形成される被膜では、要求性能
（高付着性、高耐食性）に対し、十分に満足しえるもの
ではない。However, the use of chromium compounds such as chromium rinses is not very environmentally preferable. recent years,
For the coating of metals and the like, there is an increasing demand for the use of coating compositions that do not contain chromium compounds. There is also a demand for shortening the process. It is an important issue to improve the adhesion and corrosion resistance of the formed film without containing a chromium compound. A coating film formed from a conventional coating composition containing no chromium compound is not sufficiently satisfactory for the required performance (high adhesion and high corrosion resistance).
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、実質
的にクロム化合物を含まず、被膜のキュア以前にクロム
含有溶液等でリンス処理することなく、公知のコーティ
ング組成物から形成される被膜が有する程度より、非常
にすぐれた付着性、および耐食性を有する被膜を提供す
ることにある。The object of the present invention is to form a coating film which is substantially free of chromium compounds and which is formed from a known coating composition without rinsing with a chromium-containing solution or the like before curing the coating film. Is to provide a coating having excellent adhesion and corrosion resistance than those of the above.
【０００７】[0007]
【課題を解決するための手段】本発明は、水分散性、ま
たは水溶性の有機被膜形成用樹脂と、フッ化物イオンお
よび錯フッ化物イオンから選ばれる１種または２種以上
のイオンと、亜鉛、コバルト、マンガン、ニッケル、
鉄、およびアルミニウムの金属イオンから選ばれる１種
または２種以上のイオンと、およびタングステン酸イオ
ンおよびモリブデン酸イオンから選ばれる１種または２
種のイオンとを含有しかつｐＨが１．６〜５であること
を特徴とする自己析出型水性コーティング組成物を提供
する。本発明の自己析出型水性コーティング組成物に金
属表面、例えば鉄系金属、亜鉛系金属、アルミニウム系
金属、およびマグネシウム系金属等の表面を接触させる
ことにより、該金属表面にすぐれた付着性、および耐食
性を有する樹脂被膜を形成せしめることができる。The present invention is directed to a water-dispersible or water-soluble organic film-forming resin, one or more ions selected from fluoride ions and complex fluoride ions, and zinc. , Cobalt, manganese, nickel,
One or more ions selected from metal ions of iron and aluminum, and one or two ions selected from tungstate ion and molybdate ion.
Provided is an autodeposition aqueous coating composition containing a species of ions and having a pH of 1.6 to 5. By bringing a metal surface such as an iron-based metal, a zinc-based metal, an aluminum-based metal, and a magnesium-based metal into contact with the autodeposition-type aqueous coating composition of the present invention, excellent adhesion to the metal surface, and A resin film having corrosion resistance can be formed.
【０００８】本発明は、ｐＨが約１．６〜５の酸性コー
ティング組成物であり、有機被膜形成用樹脂、フッ化物
イオンおよび／または錯フッ化物イオン、および亜鉛、
コバルト、マンガン、ニッケル、鉄、およびアルミニウ
ムの金属イオンから選ばれる１種または２種以上のイオ
ンを含み、さらにタングステン酸イオンおよび／または
モリブデン酸イオンを含有することにより、従来の自己
析出型コーティング組成物から形成される被膜よりすぐ
れた付着性、および耐食性を有する被膜を形成させるこ
とができる。The present invention is an acidic coating composition having a pH of about 1.6 to 5, which comprises an organic film forming resin, a fluoride ion and / or a complex fluoride ion, and zinc.
A conventional autodeposition coating composition containing one or more ions selected from metal ions of cobalt, manganese, nickel, iron and aluminum, and further containing tungstate ions and / or molybdate ions. It is possible to form a coating having better adhesion and corrosion resistance than a coating formed from a material.
【０００９】また本発明は、自己析出型コーティング組
成物から形成される被膜の付着性、および耐食性を改良
するための後処理（被膜のキュア以前にクロム含有溶液
等でリンス処理）をすることなく、すぐれた付着性、お
よび耐食性を有する被膜を形成させることができる。The present invention also requires no post-treatment (rinsing with a chromium-containing solution prior to curing the coating) to improve the adhesion and corrosion resistance of the coating formed from the autodeposition coating composition. A film having excellent adhesion and corrosion resistance can be formed.
【００１０】本発明で使用しうる有機被膜形成用樹脂の
一つは、例えば特開昭６１−１６８６７３に開示された
タイプの樹脂が好適に使用できる。As one of the resins for forming an organic film which can be used in the present invention, for example, a resin of the type disclosed in JP-A-61-168673 can be preferably used.
【００１１】また、本発明に使用しうる有機被膜形成用
樹脂は、メチルアクリレート、エチルアクリレート、ｎ
−ブチルアクリレート、２−ヒドロキシエチルアクリレ
ート、２−ヒドロキシプロピルアクリレート、２−エチ
ルヘキシルアクリレート、メチルメタクリレート、エチ
ルメタクリレート、ｎ−ブチルメタクリレート、２−ヒ
ドロキシエチルメタクリレート、２−ヒドロキシプロピ
ルメタクリレート、グリシジルアクリレート、グリシジ
ルメタクリレート、アクリルアミド、メタクリルアミ
ド、アクリロニトリル、エチレン、スチレン、ビニルク
ロライド、ビニリデンクロライド、ビニルアセテート、
アクリル酸、メタクリル酸等から選ばれるモノマー１種
ないしそれ以上からなる重合体樹脂、およびウレタン樹
脂、エポキシ樹脂、ポリエステル樹脂が挙げられる。The resin for forming an organic film which can be used in the present invention includes methyl acrylate, ethyl acrylate and n.
-Butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, Acrylamide, methacrylamide, acrylonitrile, ethylene, styrene, vinyl chloride, vinylidene chloride, vinyl acetate,
Polymer resins made of one or more monomers selected from acrylic acid, methacrylic acid and the like, and urethane resins, epoxy resins and polyester resins can be mentioned.
【００１２】本発明に使用する有機被膜形成用樹脂は、
アニオン性、カチオン性、ノニオン性、および両性樹脂
が挙げられ、特にその限定はない。コーティング組成物
中の好ましい樹脂固形分量は５〜５５０ｇ／ｌ、さらに
好ましくは５０〜１００ｇ／ｌの範囲である。The resin for forming an organic film used in the present invention is
Examples thereof include anionic, cationic, nonionic, and amphoteric resins, and there is no particular limitation. The preferable resin solid content in the coating composition is in the range of 5 to 550 g / l, more preferably 50 to 100 g / l.
【００１３】本発明に使用しうるフッ化物イオンおよび
錯フッ化物イオンは、ジルコンフッ化水素酸、チタンフ
ッ化水素酸、ケイフッ化水素酸、ホウフッ化水素酸、フ
ッ化水素酸、およびこれらの酸のアンモニウム塩、リチ
ウム塩、ナトリウム塩、カリウム塩等の形で供給でき
る。被覆組成物中の好ましいフッ化物イオンおよび錯フ
ッ化物イオンの含有量はフッ素として０．１〜５ｇ／
ｌ、さらに好ましくは０．５〜３ｇ／ｌの範囲である。Fluoride ions and complex fluoride ions which can be used in the present invention include zircon hydrofluoric acid, titanium hydrofluoric acid, hydrosilicofluoric acid, hydrofluoroboric acid, hydrofluoric acid, and ammonium of these acids. It can be supplied in the form of salt, lithium salt, sodium salt, potassium salt or the like. The preferred fluoride ion and complex fluoride ion content in the coating composition is 0.1-5 g / fluorine.
1 and more preferably 0.5 to 3 g / l.
【００１４】本発明のコーティング組成物は、ｐＨを約
１．６〜５の範囲に維持することが好ましい。この範囲
を大きく外れると樹脂被膜が形成されにくい傾向にあ
る。コーティング組成物のｐＨを調整するために、前記
のフッ化物イオンおよび錯フッ化物イオンを供給しうる
酸、およびそれらの塩類、さらには硝酸、リン酸および
ホウ酸から選ばれる無機酸、およびフィチン酸およびタ
ンニン酸から選ばれる有機酸から選ばれる１種または２
種以上の酸を使用できる。硝酸、リン酸、ホウ酸、フィ
チン酸、およびタンニン酸の添加は素材に対する被膜の
付着性向上に有効である。The coating composition of the present invention preferably maintains the pH in the range of about 1.6-5. If it deviates significantly from this range, it tends to be difficult to form a resin film. In order to adjust the pH of the coating composition, an acid capable of supplying the above-mentioned fluoride ion and complex fluoride ion, and salts thereof, further, an inorganic acid selected from nitric acid, phosphoric acid and boric acid, and phytic acid. And one or two selected from organic acids selected from tannic acid
More than one acid can be used. Addition of nitric acid, phosphoric acid, boric acid, phytic acid, and tannic acid is effective in improving the adhesion of the coating film to the material.
【００１５】本発明に使用する亜鉛、コバルト、マンガ
ン、ニッケル、鉄、およびアルミニウムの金属イオン
は、これらの金属の炭酸塩、硝酸塩、リン酸塩、硫酸
塩、水酸化物、酸化物、塩化物で供給することができ
る。金属イオンは、被膜形成（析出過程）で樹脂被膜中
に取り込まれ、被膜乾燥時の加熱下にて樹脂の架橋剤と
して作用している。金属イオンは、樹脂中の官能基と結
合し、樹脂の高分子化をもたらし、金属上に形成された
被膜の耐食性を向上させる。The metal ions of zinc, cobalt, manganese, nickel, iron and aluminum used in the present invention are carbonates, nitrates, phosphates, sulfates, hydroxides, oxides and chlorides of these metals. Can be supplied at. The metal ions are taken into the resin film during the film formation (precipitation process), and act as a crosslinking agent for the resin under heating when the film is dried. The metal ions combine with the functional groups in the resin to cause the resin to be polymerized, and improve the corrosion resistance of the coating film formed on the metal.
【００１６】本発明において重要な点は、有機被膜形成
用樹脂と、フッ化物イオンおよび／または錯フッ化物イ
オン、および亜鉛、コバルト、マンガン、ニッケル、
鉄、アルミニウムの金属イオンから選ばれる１種または
２種以上のイオンを含むコーティング組成物に、さらに
タングステン酸イオンおよび／またはモリブデン酸イオ
ンから選ばれる１種または２種を含有することにある。Important points in the present invention are organic film forming resin, fluoride ion and / or complex fluoride ion, zinc, cobalt, manganese, nickel,
The coating composition containing one or more kinds of ions selected from iron and aluminum metal ions further contains one or two kinds selected from tungstate ions and / or molybdate ions.
【００１７】本発明の自己析出型水性コーティング組成
物中のタングステン酸イオンまたはモリブデン酸イオン
から選ばれる１種または２種のイオンは上記金属イオン
の一部と錯体を形成し、この錯体中の金属（イオン）
は、被塗物金属の表面から溶出した金属イオンと置換
し、効率的に被塗物金属表面上に析出し、有機被膜形成
用樹脂とともに金属表面を被覆するものと推定される。One or two ions selected from tungstate ions or molybdate ions in the self-depositing aqueous coating composition of the present invention form a complex with a part of the above metal ions, and the metal in the complex is formed. (ion)
Is presumed to substitute for metal ions eluted from the surface of the metal to be coated, efficiently deposit on the surface of the metal to be coated, and coat the metal surface with the resin for forming an organic film.
【００１８】従来のクロムリンスの場合、樹脂被膜中に
取り込まれるクロム（イオン）は、樹脂被膜の比較的表
面近傍に多く存在するのに対し、タングステン酸イオン
および／またはモリブデン酸イオンを被覆組成物中に含
有することにより、形成される樹脂被膜中に取り込まれ
る金属イオンは、樹脂被膜中のみならず、従来のコーテ
ィング組成物の場合に比し、特に素材の金属表面近傍に
も多く存在し、その結果、優れた付着性、および耐食性
を有する被膜を得ることができる。In the case of the conventional chrome rinse, the chromium (ions) taken into the resin coating film are present in a large amount relatively in the vicinity of the surface of the resin coating film, whereas the tungstate ion and / or molybdate ion is used as the coating composition. By containing it, the metal ions taken into the formed resin film are not only present in the resin film, but are more often present near the metal surface of the material than in the case of the conventional coating composition, As a result, a coating having excellent adhesion and corrosion resistance can be obtained.
【００１９】本発明に使用しうるタングステン酸イオン
はタングステン酸およびタングステン酸のナトリウム、
カルシウム、カリウム塩等の形で供給できる。本発明に
使用しうるモリブデン酸イオンはモリブデン酸およびモ
リブデン酸のナトリウム、カルシウム、カリウム塩等の
形で供給できる。コーティング組成物中のタングステン
酸イオンおよびモリブデン酸イオンの含有量は、０．１
〜５ｇ／ｌ、更に好ましくは０．３〜２ｇ／ｌの範囲で
ある。Tungstate ions that can be used in the present invention are tungstic acid and sodium tungstate,
It can be supplied in the form of calcium, potassium salt or the like. Molybdate ions that can be used in the present invention can be provided in the form of molybdic acid and sodium, calcium, potassium salts of molybdic acid and the like. The content of tungstate ion and molybdate ion in the coating composition is 0.1.
˜5 g / l, more preferably 0.3 to 2 g / l.
【００２０】本発明のコーティング組成物に、必要に応
じて酸化剤を含有することもできる。また、被膜を着色
するのに顔料を含有することもできる。If desired, the coating composition of the present invention may contain an oxidizing agent. Further, a pigment may be contained to color the film.
【００２１】[0021]
【実施例】以下、本発明の実施例および比較例を説明す
る。 組成物製造例Ａ〜Ｑ アクリル系エマルジョン（固形分４１．５％）（ロープ
レックスＷＬ−９１、Ｒｏｈｍ ＆ Ｈａａｓ Ｃｏ．
製）を用い、他の成分は第１表に示す配合によって水性
コーティング組成物を調製（脱イオン水にて全量１Ｌ）
した。EXAMPLES Examples and comparative examples of the present invention will be described below. Composition Production Examples A to Q Acrylic emulsion (solid content 41.5%) (Rhoplex WL-91, Rohm & Haas Co.
A water-based coating composition was prepared according to the formulation shown in Table 1 (the total amount was 1 L with deionized water).
did.
【００２２】（実施例） 実施例１〜１６ 組成物製造例Ａ〜Ｐにより調製した水性コーティング組
成物を用い、水性コーティング組成物浴を約２０〜２２
℃に保ち、あらかじめ清浄された冷延鋼板、合金化溶融
亜鉛メッキ鋼板、電気亜鉛メッキ鋼板、又はアルミニウ
ム板（いずれも７０×１５０×１ｍｍサイズ）を１８０
秒間浸漬し、次いで水洗したのち、オーブンにて１８０
℃×２０分間乾燥後、各試験に供した。ここで得た試験
板の性能試験結果を第２表に示した。(Examples) Examples 1 to 16 Compositions Using the aqueous coating compositions prepared according to Production Examples A to P, about 20 to 22 aqueous coating composition baths were used.
Keep cold rolled steel sheet, hot-dip galvanized steel sheet, galvanized steel sheet, or aluminum sheet (70 × 150 × 1 mm in size) that has been cleaned in advance at 180 ℃
Immerse for 2 seconds, then rinse with water and then 180 in the oven
After drying at 20 ° C. for 20 minutes, each test was performed. The performance test results of the test plates obtained here are shown in Table 2.
【００２３】（比較例） 比較例１〜３ 組成物製造例Ｑにより調製した水性コーティング組成物
を用い、水性コーティング組成物浴を約２０〜２２℃に
保ち、あらかじめ清浄された冷延鋼板、合金化溶融亜鉛
メッキ鋼板、電気亜鉛メッキ鋼板（いずれも７０×１５
０×１ｍｍサイズ）を１８０秒間浸漬し、次いで水洗し
たのち、オーブンにて１８０℃×２０分間乾燥後、各試
験に供した。ここで得た試験板の性能試験結果を第２表
に示した。
Comparative Examples Comparative Examples 1 to 3 Composition Using the aqueous coating composition prepared according to Production Example Q, the aqueous coating composition bath was kept at about 20 to 22 ° C. and pre-cleaned cold-rolled steel sheet and alloy. Chemical hot-dip galvanized steel sheet, electrogalvanized steel sheet (both 70 × 15
(0 × 1 mm size) was immersed for 180 seconds, washed with water, dried in an oven at 180 ° C. for 20 minutes, and then subjected to each test. The performance test results of the test plates obtained here are shown in Table 2.
【００２４】比較例４ 組成物製造例Ｑにより調製した水性コーティング組成物
を用い、水性コーティング組成物浴を約２０〜２２℃に
保ち、あらかじめ清浄された冷延鋼板（７０×１５０×
１ｍｍサイズ）を１８０秒間浸漬し、次いで水洗したの
ち、さらにクロム含有水溶液（登録商標バーレン６０、
日本パーカライジング（株）製）に常温で６０秒間浸漬
したのち、オーブンにて１８０℃×２０分間乾燥後、各
試験に供した。ここで得た試験板の性能試験結果を第２
表に示した。Comparative Example 4 Composition Using the aqueous coating composition prepared according to Production Example Q, the aqueous coating composition bath was kept at about 20 to 22 ° C. and pre-cleaned cold rolled steel sheet (70 × 150 ×).
1 mm size) is soaked for 180 seconds and then washed with water, and then a chromium-containing aqueous solution (registered trademark Barren 60,
After dipping in Nihon Parkerizing Co., Ltd. for 60 seconds at room temperature, it was dried in an oven at 180 ° C. for 20 minutes and then subjected to each test. The performance test results of the test plate obtained here are the second
Shown in the table.
【００２５】試験方法及び判定基準 １．被膜付着性（ゴバン目テープ剥離試験） ４０℃×２４０時間温水浸漬前後の試験板に１ｍｍ四
方、１００個のますを刻み、テープ剥離し被膜の残存す
る目数を測定した。浸漬前をａ、浸漬後をｂで表示し
た。Test Method and Criteria 1. Adhesion of coating film (Rubber-eye tape peeling test) 100 mm squares of 1 mm square were carved on a test plate before and after immersion in warm water at 40 ° C. for 240 hours, and the tape was peeled off to measure the number of remaining marks of the coating film. A before immersion is indicated by a, and after immersion is indicated by b.
【００２６】２．被膜付着性（デユポン衝撃試験） ４０℃×２４０時間温水浸漬前後の試験板に直径１／２
インチで１ｋｇの垂錘を落下させた後、衝撃部をテープ
剥離した。判定は被膜が剥離しない垂錘の最大落下高さ
で表示した。上記１と同様に浸漬前をａ、浸漬後をｂで
表示した。2. Coating adhesion (Dupon impact test) 40 ° C x 240 hours 1/2 diameter on test plate before and after hot water immersion
After dropping a hanging weight of 1 kg in inches, the impact part was tape-peeled. The judgment was indicated by the maximum drop height of the hanging weight at which the coating did not peel off. As in the case of 1, the value before the immersion was indicated by a and the value after the immersion was indicated by b.
【００２７】３．耐食性 被膜に金属素地まで達するクロスカットを入れた試験板
を塩水噴霧試験（ＪＩＳＺ−２３７１）で試験した（冷
延鋼板、合金化溶融亜鉛メッキ鋼板、および電気亜鉛メ
ッキ鋼板は５００時間、アルミニウム板は１０００時
間）。試験後、テープ剥離を行った。判定はクロスカッ
ト部からの剥離巾（片側、ｍｍ）を測定した。3. Corrosion resistance A test plate with a cross cut reaching the metal substrate in the coating was tested by a salt spray test (JISZ-2371) (for cold rolled steel plate, galvannealed steel plate and galvanized steel plate for 500 hours, aluminum plate was 1000 hours). After the test, tape peeling was performed. The judgment was made by measuring the peeling width (one side, mm) from the cross-cut portion.
【００２８】[0028]
【発明の効果】本発明の自己析出型水性コーティング組
成物は、クロムを含有しないため環境上好ましい。ま
た、本発明の自己析出型水性コーティング組成物に金属
表面を接触させることにより、被膜のキュア以前にクロ
ム含有溶液等でリンス処理することなく、従来のコーテ
ィング組成物から形成される被膜が有する程度より、非
常に優れた付着性および耐食性を有する被膜が得られ
る。The autodeposition type aqueous coating composition of the present invention does not contain chromium and is environmentally preferable. Further, by bringing the metal surface into contact with the autodeposition-type aqueous coating composition of the present invention, the coating film formed from the conventional coating composition does not have to be rinsed with a chromium-containing solution before curing the coating film. This gives a coating with very good adhesion and corrosion resistance.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
Claims (2)
樹脂と、フッ化物イオンおよび錯フッ化物イオンから選
ばれる１種または２種以上のイオンと、亜鉛、コバル
ト、マンガン、ニッケル、鉄、およびアルミニウムの金
属イオンから選ばれる１種または２種以上のイオンと、
およびタングステン酸イオンおよびモリブデン酸イオン
から選ばれる１種または２種のイオンとを含有しかつｐ
Ｈが１．６〜５であることを特徴とする自己析出型水性
コーティング組成物。1. A water-dispersible or water-soluble organic film-forming resin, one or more ions selected from fluoride ions and complex fluoride ions, and zinc, cobalt, manganese, nickel and iron. , And one or more ions selected from aluminum metal ions,
And one or two ions selected from tungstate and molybdate and p
H is 1.6-5, The autodeposition type | mold aqueous coating composition characterized by the above-mentioned.
リン酸およびホウ酸から選ばれる無機酸およびフイチン
酸およびタンニン酸から選ばれる有機酸から選ばれる１
種または２種以上の酸を含む請求項１記載の自己析出型
水性コーティング組成物。2. Nitric acid as an acid for adjusting to pH 1.6 to 5,
1 selected from an inorganic acid selected from phosphoric acid and boric acid and an organic acid selected from phytic acid and tannic acid
The self-depositing aqueous coating composition according to claim 1, which comprises one or more acids.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4040571A JPH05214266A (en) | 1992-01-31 | 1992-01-31 | Self-depositing water-based coating composition |
| EP93903012A EP0624182A1 (en) | 1992-01-31 | 1993-01-15 | Autodeposition coating composition |
| PCT/US1993/000137 WO1993015154A1 (en) | 1992-01-31 | 1993-01-15 | Autodeposition coating composition |
| AU34383/93A AU3438393A (en) | 1992-01-31 | 1993-01-15 | Autodeposition coating composition |
| BR9305766A BR9305766A (en) | 1992-01-31 | 1993-01-15 | Aqueous composition of self-deposit coating and self-deposit coating |
| CA002128095A CA2128095A1 (en) | 1992-01-31 | 1993-01-15 | Autodeposition coating composition |
| MX9300330A MX9300330A (en) | 1992-01-31 | 1993-01-22 | SELF-DEPOSITION COATING COMPOSITION. |
| ZA93532A ZA93532B (en) | 1992-01-31 | 1993-01-25 | Autodeposition coating composition. |
| US08/634,132 US5646211A (en) | 1992-01-31 | 1996-04-19 | Autodeposition coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4040571A JPH05214266A (en) | 1992-01-31 | 1992-01-31 | Self-depositing water-based coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05214266A true JPH05214266A (en) | 1993-08-24 |
Family
ID=12584167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4040571A Pending JPH05214266A (en) | 1992-01-31 | 1992-01-31 | Self-depositing water-based coating composition |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0624182A1 (en) |
| JP (1) | JPH05214266A (en) |
| AU (1) | AU3438393A (en) |
| BR (1) | BR9305766A (en) |
| CA (1) | CA2128095A1 (en) |
| MX (1) | MX9300330A (en) |
| WO (1) | WO1993015154A1 (en) |
| ZA (1) | ZA93532B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010100840A1 (en) * | 2009-03-02 | 2010-09-10 | 日本パーカライジング株式会社 | Electrocoating composition and method for electrocoating |
| WO2011061784A1 (en) * | 2009-11-17 | 2011-05-26 | 日本パーカライジング株式会社 | Surface-treatment liquid for autodeposition coating of iron-based and/or zinc-based metal material and surface-treatment method |
| JP2014505763A (en) * | 2010-12-20 | 2014-03-06 | 日本パーカライジング株式会社 | Autodeposition coating for improving glossy appearance and method for applying the coating |
| WO2015015971A1 (en) * | 2013-07-31 | 2015-02-05 | 日本パーカライジング株式会社 | Self-depositing coating composition for numerous kinds of metal materials, manufacturing method therefor, metal material with organic resin film, and manufacturing method therefor |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5328525A (en) * | 1993-01-05 | 1994-07-12 | Betz Laboratories, Inc. | Method and composition for treatment of metals |
| NL1000118C2 (en) * | 1995-04-11 | 1996-10-14 | Adw Chem Prod Bv | Chromium-free coating composition for metal surface treatment and method using it. |
| DE19755421A1 (en) | 1997-12-13 | 1999-06-17 | Henkel Kgaa | Rubber-metal composite |
| US6476119B1 (en) | 1998-01-27 | 2002-11-05 | Lord Corporation | Aqueous primer or coating |
| US7037385B2 (en) | 1998-01-27 | 2006-05-02 | Lord Corporation | Aqueous metal treatment composition |
| WO1999037722A1 (en) | 1998-01-27 | 1999-07-29 | Lord Corporation | Aqueous metal treatment composition |
| US6902766B1 (en) | 2000-07-27 | 2005-06-07 | Lord Corporation | Two-part aqueous metal protection treatment |
| US7294211B2 (en) | 2002-01-04 | 2007-11-13 | University Of Dayton | Non-toxic corrosion-protection conversion coats based on cobalt |
| US20030172998A1 (en) * | 2002-03-14 | 2003-09-18 | Gerald Wojcik | Composition and process for the treatment of metal surfaces |
| CN104685099A (en) | 2012-08-29 | 2015-06-03 | Ppg工业俄亥俄公司 | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
| AU2013309270B2 (en) | 2012-08-29 | 2016-03-17 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| RU2729485C1 (en) | 2016-08-24 | 2020-08-07 | Ппг Индастриз Огайо, Инк. | Iron-containing cleaner composition |
| EP4310223A1 (en) | 2022-07-18 | 2024-01-24 | Henkel AG & Co. KGaA | Alkaline reaction rinse for decorative autophoretic coatings |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5344949B2 (en) * | 1973-03-02 | 1978-12-02 | ||
| AT352843B (en) * | 1978-04-27 | 1979-10-10 | Vianova Kunstharz Ag | PROCESS FOR THE PREPARATION OF AQUATIC COATING EMULSIONS |
| EP0046268A3 (en) * | 1980-08-14 | 1982-08-04 | Union Carbide Corporation | Corrosion resistant autodeposition composition |
| EP0312648A3 (en) * | 1983-07-25 | 1989-05-10 | HENKEL CORPORATION (a Delaware corp.) | Vinylidene chloride latex in autodeposition and low temperature cure |
-
1992
- 1992-01-31 JP JP4040571A patent/JPH05214266A/en active Pending
-
1993
- 1993-01-15 EP EP93903012A patent/EP0624182A1/en not_active Withdrawn
- 1993-01-15 BR BR9305766A patent/BR9305766A/en not_active Application Discontinuation
- 1993-01-15 CA CA002128095A patent/CA2128095A1/en not_active Abandoned
- 1993-01-15 WO PCT/US1993/000137 patent/WO1993015154A1/en not_active Application Discontinuation
- 1993-01-15 AU AU34383/93A patent/AU3438393A/en not_active Abandoned
- 1993-01-22 MX MX9300330A patent/MX9300330A/en unknown
- 1993-01-25 ZA ZA93532A patent/ZA93532B/en unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010100840A1 (en) * | 2009-03-02 | 2010-09-10 | 日本パーカライジング株式会社 | Electrocoating composition and method for electrocoating |
| JP2010202740A (en) * | 2009-03-02 | 2010-09-16 | Nippon Parkerizing Co Ltd | Electrodeposition coating composition and electrodeposition coating method |
| WO2011061784A1 (en) * | 2009-11-17 | 2011-05-26 | 日本パーカライジング株式会社 | Surface-treatment liquid for autodeposition coating of iron-based and/or zinc-based metal material and surface-treatment method |
| JP2014505763A (en) * | 2010-12-20 | 2014-03-06 | 日本パーカライジング株式会社 | Autodeposition coating for improving glossy appearance and method for applying the coating |
| WO2015015971A1 (en) * | 2013-07-31 | 2015-02-05 | 日本パーカライジング株式会社 | Self-depositing coating composition for numerous kinds of metal materials, manufacturing method therefor, metal material with organic resin film, and manufacturing method therefor |
| JP2015030864A (en) * | 2013-07-31 | 2015-02-16 | 日本パーカライジング株式会社 | Self-precipitation type coating composition for multi-metal materials, method of producing the same, metal material having organic resin coat and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3438393A (en) | 1993-09-01 |
| EP0624182A1 (en) | 1994-11-17 |
| WO1993015154A1 (en) | 1993-08-05 |
| ZA93532B (en) | 1993-08-26 |
| BR9305766A (en) | 1997-01-28 |
| CA2128095A1 (en) | 1993-08-05 |
| MX9300330A (en) | 1993-12-31 |
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